A Luminescent Thermometer Exhibiting Slow Relaxation of the Magnetization: Toward Self-Monitored Building Blocks for Next-Generation Optomagnetic Devices.

The development and integration of Single-Molecule Magnets (SMMs) into molecular electronic devices continue to be an exciting challenge. In such potential devices, heat generation due to the electric current is a critical issue that has to be considered upon device fabrication. To read out accurately the temperature at the submicrometer spatial range, new multifunctional SMMs need to be developed. Herein, we present the first self-calibrated molecular thermometer with SMM properties, which provides an elegant avenue to address these issues. The employment of 2,2'-bipyrimidine and 1,1,1-trifluoroacetylacetonate ligands results in a dinuclear compound, [Dy2(bpm)(tfaa)6], which exhibits slow relaxation of the magnetization along with remarkable photoluminescent properties. This combination allows the gaining of fundamental insight in the electronic properties of the compound and investigation of optomagnetic cross-effects (Zeeman effect). Importantly, spectral variations stemming from two distinct thermal-dependent mechanisms taking place at the molecular level are used to perform luminescence thermometry over the 5-398 K temperature range. Overall, these properties make the proposed system a unique molecular luminescent thermometer bearing SMM properties, which preserves its temperature self-monitoring capability even under applied magnetic fields.

Strong ferromagnetic exchange coupling in a {Ni} cluster mediated through an air-stable tetrazine-based radical anion.

A planar tetradentate 3,6-bis(2-pyrimidyl)-1,2,4,5-tetrazine (BpymTz) templating chelate affords the formation of an unprecedented BpymTz˙- radical anion bridged {Ni} complex. Detailed magnetic measurements performed on the isolated air stable [Ni(BpymTz˙-)Cl6(DMF)8]Cl·0.5(H2O) compound reveal strong ferromagnetic NiII-BpymTz˙- interactions with a coupling constant of J = 98.84 cm-1.

From discrete molecule, to polymer, to MOF: mapping the coordination chemistry of Cd(II) using (113)Cd solid-state NMR.

Studies of three related Cd(II) systems (a discrete [Cd(II)2] unit, a one-dimensional [Cd(II)2]n coordination polymer and a Cd(II)-based MOF) all derived from the ligand 2,4,6-tris(2-pyrimidyl)-1,3,5-triazine, reveal an exceptionally rare example of (113)Cd-(113)Cd J coupling in the polymer that is detectable by solid-state NMR ((2)JCd-Cd = ∼65 Hz).

[U(bipy)4 ]: A Mistaken Case of U0 ?

After more than 50 years, the synthesis and electronic structure of the first and only reported "U0 complex" [U(bipy)4 ] (1) has been reinvestigated. Additionally, its one-electron reduced product [Na(THF)6 ][U(bipy)4 ] (2) has been newly discovered. High resolution crystallographic analyses combined with magnetic and computational data show that 1 and its derivative 2 are best described as highly reduced species containing mid-to-high-valent uranium ligated by redox non-innocent ligands.

Iodine(III)-Mediated para-Selective Direct Imidation of Anilides.

The direct, nucleophilic imidation of acetanilide derivatives has been performed under mild, iodine(III)-mediated or -catalyzed conditions, employing lithium triflimide as the nitrogen source. The reaction exhibits exclusive regioselectivity for the para position and shows a good tolerance for varied functional groups at both the ortho or meta positions. Preliminary mechanistic data suggest that the LiNTf2 reagent plays a key role in the reactivity.

Anion-induced Ag(I) self-assemblies with electron deficient aromatic ligands: anion-π-system interactions as a driving force for templated coordination networks.

Three novel 1D, 2D and 3D coordination polymers were successfully isolated using nitrogen based 3,6-bis(2'-pyrimidyl)-1,2,4,5-tetrazine (BPymTz) and 2,4,6-tris(2-pyrimidyl)-1,3,5-triazine (TPymT) ligands with Ag(I) ions. The formation of these supramolecular assemblies was templated through anion-π-system interactions.

Unprecedented trinuclear Ag(I) complex with 2,4,6-tris(2-pyrimidyl)-1,3,5-triazine as an efficient catalyst for the aziridination of olefins.

An unprecedented trinuclear heteroleptic Ag(I) complex was isolated using a stable multidentate 2,4,6-tris(2-pyrimidyl)-1,3,5-triazine (TPymT) ligand. The obtained compound is an efficient catalyst for the direct aziridination of terminal olefins.

Oxidative para-triflation of acetanilides.

Direct triflation of acetanilide derivatives with silver triflate has been accomplished under mild iodine(III)-mediated oxidative conditions. The reaction shows excellent regioselectivity for the para position and tolerates a range of ortho and meta substituents on the aromatic ring. This method is also compatible with the preparation of arylnonaflates in synthetically useful yields.